Reactive oxygen species in biological media are they friend or foe? Major In vivo and In vitro sensing challenges.

The role of Reactive Oxygen Species (ROS) on biological media has been shifting over the years, as the knowledge on the complex mechanism that lies in underneath their production and overall results has been growing. It has been known for some time that these species are associated with a number of health conditions. However, they also participate in the immunoactivation cascade process, and can have an active role in theranostics. Macrophages, for example, react to the presence of pathogens through ROS production, potentially allowing the development of new therapeutic strategies. However, their short lifetime and limited spatial distribution of ROS have been limiting factors to the development and understanding of this phenomenon. Even though, ROS have shown successful theranostic applications, e.g., photodynamic therapy, their wide applicability has been hampered by the lack of effective tools for monitoring these processes in real time. Thus the development of innovative sensing strategies for in vivo monitoring of the balance between ROS concentration and the resultant immune response is of the utmost relevance. Such knowledge could lead to major breakthroughs towards the development of more effective treatments for neurodegenerative diseases. Within this review we will present the current understanding on the interaction mechanisms of ROS with biological systems and their overall effect. Additionally, the most promising sensing tools developed so far, for both in vivo and in vitro tracking will be presented along with their main limitations and advantages. This review focuses on the four main ROS that have been studied these are: singlet oxygen species, hydrogen peroxide, hydroxyl radical and superoxide anion.

Carbon dots as Reactive Nitrogen Species nanosensors.

Three sets of Carbon Dots (Cdots) were produced through the carbohydrates acid thermal decomposition method. These nanoparticles were functionalized with a polymer, known for its biological compatibility: polyethylene glycol, PEG200, and folic acid, FA, a biomolecule associated with the reactive oxygen and nitrogen (ROS/RNS) savaging process, thus resulting CdotsPEG200, CdotsPEG200FA and CdotsFA. These nanoparticles were tested as nitric oxide radical (NO·) sensors and it was determined that CdotsPEG200FA and CdotsFA fluorescence intensity was quenched by the presence of this radical specie. Moreover, according to the Benesi-Hilderbrand plot, the nanoparticles have a high affinity towards the analyte and this interaction is consistent with a 1:1 stoichiometry, through an independent mechanism. The Stern-Volmer constant, obtained for both sensing systems, is compatible with the formation of stable complexes (static quenching) between the Folic Acid residues on the Cdots surface and NO·. The detection and quantification limits along with the sensitivity were calculated for both nanoparticles: DL (31.7 ± 0.02) x 10-9, QL (96.29 ± 0.01) x 10-9, Sensitivity (5.2 ± 0.5) x 109 M for CdotsFA and DL (83 ± 3) x 10-10, QL (251 ± 2) x 10-10, Sensitivity (8.4 ± 0.3) x 1010 M. These values are adequate for biological sensing and are quite competitive with other reported nanosensors for NO· detection and quantification.

Novel Highly Luminescent Amine-Functionalized Bridged Silsesquioxanes.

Amine-functionalized bridged silsesquioxanes (BSs) were synthesized from bis[(3-trimethoxysilyl)propyl] amine via a solvent-mediated route. BS-1 and BS-2 were obtained at neutral pH with sub- and stoichiometric amounts of water, respectively, and high tetrahydrofuran content. BS-3 was prepared with hyperstoichiometric water concentration, high tetrahydrofuran content, and hydrochloric acid. BS-4 was synthesized with hyperstoichiometric water concentration, high ethanol content, and sodium hydroxide. BS-1 and BS-2 were produced as transparent films, whereas BS-3 and BS-4 formed white powders. Face-to-face stacking of flat or folded lamellae yielded quasi-hydrophobic platelets with emission quantum yields of 0.05 ± 0.01 (BS-1 and BS-2) or superhydrophilic onion-like nanoparticles with exciting emission quantum yields of 0.38 ± 0.03 (BS-3) and 0.33 ± 0.04 (BS-4), respectively. The latter two values are the largest ever reported for amine-functionalized siloxane-based hybrids lacking aromatic groups. Fast Grotthus proton hopping between = [Formula: see text]/ = NH groups (BS-3) and = N-/ = NH groups (BS-4), promoted by H+ and OH- ions, respectively, and aided by short amine-amine contacts provided by the onion-like morphology, account for this unique optical behavior.